CN116960369A - Cathode catalytic layer structure for membrane electrode of fuel cell and preparation method thereof - Google Patents

Cathode catalytic layer structure for membrane electrode of fuel cell and preparation method thereof Download PDF

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CN116960369A
CN116960369A CN202210409434.1A CN202210409434A CN116960369A CN 116960369 A CN116960369 A CN 116960369A CN 202210409434 A CN202210409434 A CN 202210409434A CN 116960369 A CN116960369 A CN 116960369A
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catalytic layer
slurry
platinum
cathode
layer structure
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陈必成
张旭
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Robert Bosch GmbH
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Robert Bosch GmbH
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Priority to DE102023203288.0A priority patent/DE102023203288A1/en
Priority to US18/301,325 priority patent/US20230335755A1/en
Publication of CN116960369A publication Critical patent/CN116960369A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
    • H01M4/8642—Gradient in composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The application provides a method for preparing a cathode catalytic layer structure of a membrane electrode assembly of a fuel cell. The method includes forming a cathode catalytic layer structure having at least a first catalytic layer and a second catalytic layer, the second catalytic layer for positioning closer to the proton exchange membrane of the membrane electrode assembly than the first catalytic layer, the first catalytic layer formed from a first slurry, and the second catalytic layer formed from a second slurry. The method includes selecting an average particle size of the platinum-based catalyst, a specific surface area of the carbon support, an I/C ratio, and a weight percentage of the platinum-based catalyst to a total weight of the carbon support and the platinum-based catalyst in the first slurry and the second slurry. The application also provides a cathode catalytic layer structure prepared by the method. According to the application, the aggregation of platinum catalyst particles and the corrosion of a carbon carrier on the cathode catalytic layer structure can be effectively reduced while the overall proton conductivity, oxygen transport capacity and ECSA of the cathode catalytic layer structure are maximized.

Description

Cathode catalytic layer structure for membrane electrode of fuel cell and preparation method thereof
Technical Field
The present application relates generally to the field of fuel cells, and in particular to a method of preparing a cathode catalytic layer structure for a membrane electrode of a fuel cell, and a cathode catalytic layer structure prepared by such a method.
Background
Power generation using electrochemical reaction of fuel and oxidantIs increasingly being used to provide electrical power, particularly in the field of electric vehicles. Proton Exchange Membrane Fuel Cells (PEMFC) are a widely used fuel cell that uses hydrogen as a fuel and oxygen as an oxidant. The Membrane Electrode Assembly (MEA) of the PEMFC consists of a polymer dielectric membrane (i.e., proton exchange membrane), catalytic Layers (CL) on both sides of the membrane, and diffusion layers (GDL). Electrochemical reactions of PEMFCs occur in the MEA, mainly involving a Hydrogen Oxidation (HOR) process and an oxygen reduction (ORR) process. H 2 And O 2 Is transmitted into the anode catalytic layer and the cathode catalytic layer through the anode diffusion layer and the cathode diffusion layer respectively, H 2 Losing electrons under the action of anode catalyst on anode catalytic layer to form H + 。H + Is transferred to the cathode side through the proton exchange membrane and is reacted with O under the action of a cathode catalyst at a cathode catalytic layer 2 Combine into H 2 O。H 2 The O is transferred into the flow field through the diffusion layer and then discharged out of the PEMFC. The electrons flow through an external circuit to the cathode to form a current.
The ORR process is a key to determine the electrochemical reaction rate of PEMFCs. The cathode catalytic layer, as an occurrence of the ORR process, its construction and composition will directly affect the performance and lifetime of the MEA, and thus the PEMFC. Accordingly, there is always a need in the industry to adjust the configuration and composition of the cathode catalytic layer to improve the performance and lifetime of the MEA.
Disclosure of Invention
The present application aims to provide an improved method of preparing the cathode catalytic layer structure of a membrane electrode assembly of a fuel cell to improve the performance and lifetime of the MEA by adjusting the configuration and composition of the cathode catalytic layer.
According to one aspect of the present application, there is provided a method of preparing a cathode catalytic layer structure of a membrane electrode assembly of a fuel cell, characterized in that the method comprises forming a cathode catalytic layer structure having at least a first catalytic layer and a second catalytic layer for positioning closer to a proton exchange membrane of the membrane electrode assembly than the first catalytic layer, the first catalytic layer being formed of a first slurry and the second catalytic layer being formed of a second slurry, wherein: (1) By a means ofThe first average particle size of the first platinum-based catalyst in the first slurry is less than the second average particle size of the second platinum-based catalyst in the second slurry; (2) The first specific surface area of the first carbon support in the first slurry is greater than or equal to 200m 2 And a second specific surface area of the second carbon support in the second slurry of 200m or less 2 /g; (3) The first I/C ratio in the first slurry is greater than 0.9, and the second I/C ratio in the second slurry is less than or equal to 0.9; and (4) a first weight percentage of the first platinum-based catalyst in the first slurry that is 40% or more of the total weight of the first carbon support and the first platinum-based catalyst, and a second weight percentage of the second platinum-based catalyst in the second slurry that is 40% or less of the total weight of the second carbon support and the second platinum-based catalyst.
In some embodiments, the first slurry and the second slurry are in at least one of the following forms: the first average particle diameter is 2nm or less, and the second average particle diameter is 2nm or more; the first specific surface area is 800m 2 /g to 1000m 2 Between/g, and the second specific surface area is 100m 2 /g to 200m 2 Between/g; the first I/C ratio is greater than 0.9 and equal to or less than 1.05, and the second I/C ratio is equal to 0.9, preferably equal to or less than 0.8; the first weight percent is between 50% and 60%, and the second weight percent is between 20% and 40%.
In some embodiments, the first platinum loading of the first catalytic layer is at least 1.5 times the second platinum loading of the second catalytic layer, the total platinum loading of the first catalytic layer and the second catalytic layer preferably being in the range of 0.1-0.6mg/cm 2 。
In some embodiments, the thickness of the first catalytic layer and the thickness of the second catalytic layer are substantially the same, and the total thickness of the first catalytic layer and the second catalytic layer is preferably 6 μm to 15 μm.
In some embodiments, the first ionomer EW value in the first slurry is greater than the second ionomer EW value in the second slurry, preferably the first ionomer EW value is between 800g/mol and 1000g/mol, and the second ionomer EW value is between 720g/mol and 800 g/mol.
In some embodiments, forming the cathode catalytic layer structure further comprises forming a third catalytic layer between the first catalytic layer and the second catalytic layer, the third catalytic layer formed from a third slurry, wherein: (1) A third average particle diameter of a third platinum-based catalyst in the third slurry is greater than the first average particle diameter and less than the second average particle diameter; (2) A third specific surface area of a third carbon support in the third slurry is greater than the second specific surface area and is greater than or equal to the first specific surface area; (3) A third I/C ratio in the third slurry is greater than the second I/C ratio and less than the first I/C ratio; (4) The weight of the third platinum-based catalyst in the third slurry is greater than or equal to 40% of the total weight of the third carbon support and the third platinum-based catalyst; and (5) the third platinum loading of the third catalytic layer is at least twice the first platinum loading of the first catalytic layer and at least twice the second platinum loading of the second catalytic layer.
In some embodiments, the first slurry, the second slurry, and the third slurry are in the form of at least one of: the first average particle size is less than 2nm, the second average particle size is greater than 4nm, and the third average particle size is between 2nm and 4 nm; the first specific surface area is 200m 2 /g to 800m 2 Between/g, the second specific surface area is 100m 2 /g to 200m 2 Between/g, and the third specific surface area is 800m 2 /g to 1000m 2 Between/g; the first I/C ratio is greater than 0.9 and equal to or less than 1.05, the second I/C ratio is equal to or less than 0.8, and the third I/C ratio is equal to 0.9; the first ionomer in the first slurry has an EW value greater than the second ionomer in the second slurry and greater than the third ionomer in the third slurry, preferably the first ionomer has an EW value between 800g/mol and 1000g/mol, the second ionomer has an EW value between 720g/mol and 800g/mol, and the third ionomer has an EW value between 720g/mol and 8 g/molBetween 00 g/mol.
In some embodiments, the total platinum loading of the first catalytic layer, the second catalytic layer, and the third catalytic layer is from 0.1 to 0.6mg/cm 2 。
In some embodiments, the thickness of each of the first, second and third catalytic layers is substantially the same, and the total thickness of the first, second and third catalytic layers is preferably 6 to 15 μm.
In some embodiments, each of the first, second, and third platinum-based catalysts is selected from the group consisting of a pure platinum catalyst and a platinum-based alloy catalyst, preferably the first, second, and third platinum-based catalysts are the same platinum-based catalyst.
In some embodiments, the cathode catalytic layer structure is formed by a transfer method, a knife coating method, a spray coating method, a brush coating method, an inkjet printing method, or a slot die coating method.
According to another aspect of the present application, there is provided a cathode catalytic layer structure for a membrane electrode assembly of a fuel cell, the cathode catalytic layer structure being prepared by the method according to the foregoing.
The preparation method provided by the application can effectively reduce the agglomeration of platinum catalyst particles and the corrosion of a carbon carrier on the cathode catalytic layer structure while maximizing the proton conductivity, oxygen transport capacity and ECSA of the whole cathode catalytic layer structure, thereby effectively improving the performance and the service life of the MEA.
Drawings
The foregoing and other aspects of the application will be more fully understood and appreciated in conjunction with the following drawings. It should be noted that the figures are merely schematic and are not drawn to scale. In the drawings:
fig. 1 schematically illustrates a cell of an electric stack of an exemplary fuel cell in which a cathode catalyst layer structure prepared by the method of preparing a cathode catalyst layer structure of a membrane electrode assembly of a fuel cell according to the present application can be used;
fig. 2 schematically shows a cathode catalytic layer structure prepared by a preparation method according to a preferred embodiment of the present application; and
fig. 3 schematically shows a cathode catalytic layer structure prepared by a preparation method according to another preferred embodiment of the present application.
Detailed Description
Some preferred embodiments of the present application are described in detail below in conjunction with examples. It will be appreciated by those skilled in the art that these examples are illustrative only and are not meant to be limiting in any way. Furthermore, features in embodiments of the application may be combined with each other without conflict. In the drawings, other components are omitted for brevity, but this does not indicate that the cell and cathode catalytic layer structure of the present application may not include other structures and/or components. It should be understood that the dimensions, proportions and number of parts of the figures are not intended to limit the application.
Fuel cell systems may be used in vehicles to provide electrical power to drive vehicle motors to provide power or to cause on-board systems to perform various functions. Fig. 1 schematically shows one cell unit 100 of a stack of an exemplary fuel cell, which is a Proton Exchange Membrane Fuel Cell (PEMFC), and the stack of which is formed by stacking a plurality of cell units 100. As will be described in detail below, the cathode catalytic layer structure prepared by the method of preparing a cathode catalytic layer structure of a membrane electrode assembly of a fuel cell according to the present application can be used in the battery cell 100.
As shown in fig. 1, the battery unit 100 generally consists of a cathode plate 101, an anode plate 103, a proton exchange membrane 105, a cathode diffusion layer 107 and a cathode catalytic layer structure 109 between the cathode plate 101 and the proton exchange membrane 105, an anode diffusion layer 111 and an anode catalytic layer structure 113 between the anode plate 103 and the proton exchange membrane 105. The cathode diffusion layer 107, the cathode catalytic layer structure 109, the anode diffusion layer 111, the anode catalytic layer structure 113 are typically made integral with the proton exchange membrane 105 and are referred to as a Membrane Electrode Assembly (MEA). The cathode diffusion layer 107 and the anode diffusion layer 111 serve to support the cathode catalytic layer structure 109 and the anode catalytic layer structure 113, respectively, and transport reaction gases and products (hydrogen, oxygen/air, water, etc.). A cathode flow field (not shown) and an anode flow field (also not shown) are formed on the cathode plate 101 and the anode plate 103, respectively. The cathode flow fields of the cathode plates 101 of the plurality of battery cells 100 constitute a cathode flow channel (not shown) of the stack 101, and the anode flow fields of the anode plates 103 of the plurality of battery cells 100 constitute an anode flow channel (also not shown) of the stack 101.
Electrochemical reactions of PEMFCs occur in the MEA, mainly involving a Hydrogen Oxidation (HOR) process and an oxygen reduction (ORR) process. H 2 And O 2 Is transmitted into the anode catalytic layer structure 113 and the cathode catalytic layer structure 109 through the anode diffusion layer 111 and the cathode diffusion layer 107 respectively, H 2 Losing electrons at the anode catalyst layer structure 113 under the action of the anode catalyst to form H + 。H + Is transferred to the cathode side through the proton exchange membrane 105 and is reacted with O at the cathode catalyst layer structure 109 under the action of the cathode catalyst 2 Combine into H 2 O。H 2 O is transferred into the cathode flow field and the anode flow field through the cathode diffusion layer 107 and the anode diffusion layer 111, and then is discharged out of the PEMFC through the cathode flow channel and the anode flow channel. The electrons then flow through an external circuit (not shown) to the cathode to form a current.
As previously mentioned, the ORR process is critical in determining the electrochemical reaction rate of PEMFCs. The cathode catalytic layer structure 109, as an occurrence of the ORR process, its construction and composition will directly affect the performance and lifetime of the MEA, and thus of the PEMFC. In order to improve the performance and lifetime of the MEA, the inventors propose an improved method of preparing a cathode catalytic layer structure for the MEA. This preparation method will be described in detail with reference to fig. 2 and 3.
Fig. 2 schematically shows a cathode catalytic layer structure 200 prepared by a preparation method according to a preferred embodiment of the application. As shown in fig. 2, the cathode catalytic layer structure 200 includes a first catalytic layer 201 and a second catalytic layer 202. The first catalytic layer 201 abuts the second catalytic layer 202 and the second catalytic layer 202 abuts the proton exchange membrane 105. That is, the second catalytic layer 202 is positioned closer to the proton exchange membrane 105 of the MEA than the first catalytic layer 201. The method of preparing the cathode catalytic layer structure 200 includes forming the cathode catalytic layer structure 200 having a first catalytic layer 201 and a second catalytic layer 202, wherein the first catalytic layer 201 is formed from a first slurry and the second catalytic layer 202 is formed from a second slurry.
As will be described in detail below, the inventors adjust the characteristics of the first and second catalytic layers 201 and 202 by adapting various parameters of the first and second slurries to effectively mitigate platinum-based catalyst particle agglomeration and carbon support corrosion on the cathode catalytic layer structure 200 while maximizing the proton conductivity, oxygen transport capacity and ECSA of the cathode catalytic layer structure 200 as a whole, thereby effectively improving the performance and lifetime of the MEA, which would otherwise result in degradation of the cathode catalytic layer structure 200 and MEA performance and lifetime.
As used in the present application and as known in the art, the slurry may also be referred to as a "catalyst slurry" or "catalyst ink" which is obtained by dispersing a catalyst into a specific solvent and homogenizing the slurry by a homogenizing dispersing device. As used herein, "specific surface area" refers to the total area of a mass of material in m 2 And/g. As used herein, "I/C ratio" refers to the mass ratio of ionomer to carbon in the slurry. It should be understood that the ionomer is, for example, nafion resin. As used herein, "ionomer EW value" refers to the weight of polymer in g/mol required to provide 1 mole of exchangeable protons. As used herein, "platinum loading" refers to the amount of platinum per unit area in mg/cm 2 . As used herein, "electrochemically active area (ECSA)" refers to the effective area in m where the electrochemical reaction actually occurs 2 /g。
Example 1:
in the foregoing production method, the first slurry and the second slurry may be configured so as to have the following characteristic parameters: (1) The first average particle size of the first platinum-based catalyst in the first slurry is smaller than the second average particle size of the second platinum-based catalyst in the second slurryThe method comprises the steps of carrying out a first treatment on the surface of the (2) The first carbon support in the first slurry has a first specific surface area of 200m or more 2 /g (e.g., the first carbon support is such asXC72, or the like), and a second specific surface area of the second carbon support in the second slurry is 200m or less 2 /g (e.g., the second carbon support is graphitized carbon), e.g., the first specific surface area may be greater than the second specific surface area; (3) The first I/C ratio in the first slurry is greater than 0.9, and the second I/C ratio in the second slurry is less than or equal to 0.9, that is, the first I/C ratio is greater than the second I/C ratio; and (4) a first weight percentage of the first platinum-based catalyst in the first slurry that is 40% or more of the total weight of the first carbon support and the first platinum-based catalyst, and a second weight percentage of the second platinum-based catalyst in the second slurry that is 40% or less of the total weight of the second carbon support and the second platinum-based catalyst, e.g., the first weight percentage may be greater than the second weight percentage.
Compared to a manufacturing method in which only one or some of the above-described characteristic parameters are adjusted, the first and second catalytic layers 201 and 202 formed of the first and second pastes having the combination of the above-described characteristic parameters (1) to (4) can effectively reduce agglomeration of platinum-based catalyst particles and corrosion of the carbon support on the cathode catalytic layer structure while maximizing the proton conductivity, oxygen transport capacity, and ECSA of the whole cathode catalytic layer structure 200.
Specifically, for a cathode catalytic layer structure 200 having two catalytic layers, the second catalytic layer 202 is positioned closer to the proton exchange membrane 105 of the MEA than the first catalytic layer 201. During the electrochemical reaction, the oxygen transmission path from the cathode flow channel to the first catalytic layer 201 is shorter than that of the second catalytic layer 202, and thus the first catalytic layer 201 is easier to obtain sufficient oxygen. However, the proton conduction path from the proton exchange membrane 105 to the first catalytic layer 201 is longer than that of the second catalytic layer 202, and thus the amount of protons that can be obtained by the first catalytic layer 201 is limited. In addition, the degree of agglomeration of the platinum-based catalyst particles and corrosion of the carbon support on the second catalytic layer 202 is more severe than that of the first catalytic layer 201. By having the first catalytic layer 201 and the second catalytic layer 202 formed of the aforementioned first slurry and second slurry, respectively, it is possible to provide the first catalytic layer 201 with better oxygen transport capability and larger ECSA, and the second catalytic layer 202 with better proton conduction capability and capability of inhibiting agglomeration of platinum-based catalyst particles and corrosion of carbon carriers, thereby effectively reducing agglomeration of platinum-based catalyst particles and corrosion of carbon carriers on the cathode catalytic layer structure 200 while maximizing the proton conduction capability, oxygen transport capability, and ECSA of the whole cathode catalytic layer structure 200. This can improve the performance and lifetime of the MEA, and thus the PEMFC.
Thus, the method of making the present application includes forming a cathode catalytic layer structure 200 having a first catalytic layer 201 and a second catalytic layer 202, the second catalytic layer 202 being for positioning closer to the proton exchange membrane 105 of the MEA than the first catalytic layer 201. The first catalytic layer 201 is formed of the aforementioned first slurry, and the second catalytic layer 202 is formed of the aforementioned second slurry.
Table 1 shows an exemplary implementation of embodiment 1.
TABLE 1
In the exemplary implementation shown in table 1, the first average particle size of the first platinum-based catalyst in the first slurry is less than the second average particle size of the second platinum-based catalyst in the second slurry. The first average particle diameter is 2nm or less, and the second average particle diameter is 2nm or more. Preferably, the first average particle size is 2nm and the second average particle size is 3nm, 4nm, 5nm or any value in between.
The first carbon support in the first slurry has a first specific surface area of 200m or more 2 /g, and the second specific surface area of the second carbon support in the second slurry is less than or equal to 200m 2 And/g. For example, the first specific surface area may be greater than the second specific surface area. Preferably, the first specific surface area is 800m 2 /g to 1000m 2 Between/g, and a second specific surface area of 100m 2 /g to 200m 2 Between/g.
The first I/C ratio in the first slurry is greater than 0.9, and the second I/C ratio in the second slurry is less than or equal to 0.9. Preferably, the first I/C ratio is greater than 0.9 and less than or equal to 1.05, and the second I/C ratio is equal to 0.9. More preferably, the second I/C ratio is 0.8 or less.
The first weight percentage of the first platinum-based catalyst in the first slurry is 40% or more based on the total weight of the first carbon support and the first platinum-based catalyst, and the second weight percentage of the second platinum-based catalyst in the second slurry is 40% or less based on the total weight of the second carbon support and the second platinum-based catalyst. For example, the first weight percent may be greater than the second weight percent. Preferably, the first weight percentage is between 50% and 60%, and the second weight percentage is between 20% and 40%. More preferably, the first weight percent is 50%, 55%, or 60%. More preferably, the second weight percent is 20%, 30% or 40%.
In an additional example, the first slurry and the second slurry may also be formulated to additionally have the following characteristic parameters: the first ionomer EW value in the first syrup is greater than the second ionomer EW value in the second syrup. In this way, it is possible to ensure good proton conduction at the first catalytic layer 201 and simultaneously ensure good proton conduction and oxygen transport at the second catalytic layer 202. Table 2 shows one exemplary implementation of this example.
TABLE 2
Preferably, the first ionomer has an EW value between 800g/mol and 1000g/mol and the second ionomer has an EW value between 720g/mol and 800 g/mol.
Furthermore, in another additional example, the first platinum loading of the first catalytic layer may be at least 1.5 times the second platinum loading of the second catalytic layer. Providing such a platinum loading gradient can be found in the firstA larger ECSA is provided at the catalytic layer 201. Preferably, the total platinum loading of the first catalytic layer and the second catalytic layer is 0.1-0.6mg/cm 2 。
Further, the thickness of the first catalytic layer 201 and the thickness of the second catalytic layer 202 may be substantially the same. Preferably, the total thickness of the first catalytic layer 201 and the second catalytic layer 202 is 6 μm to 15 μm.
Comparative example 1:
a cathode catalytic layer structure formed from the slurries shown in table 3. It should be understood that as a comparative example, the remaining parameters of the cathode catalytic layer structure, not listed, were consistent with those of the cathode catalytic layer structure 200 formed from the slurries shown in table 1.
TABLE 3 Table 3
In the accelerated aging test, a dynamic voltage square wave scan of 0.6 to 0.95V was applied to the cathode side for a period of 2s for a total cycle of 30000 turns. After 30000 cycles, the ECSA of the cathode catalytic layer structure 200 formed from the slurry shown in table 1 decreased by less than 30%, while the cathode catalytic layer structure of comparative example 1 exceeded 40%. It can be seen that the cathode catalytic layer structure 200 has higher durability and longer service life than the comparative example. The cathode catalytic layer structure 200 prepared by the preparation method of the application effectively reduces the agglomeration of platinum catalyst particles and the corrosion of a carbon carrier on the cathode catalytic layer structure while maximizing the proton conductivity, oxygen transport capacity and ECSA of the whole cathode catalytic layer structure.
Fig. 3 schematically shows a cathode catalytic layer structure 300 prepared by a preparation method according to another preferred embodiment of the present application. As shown in fig. 3, the cathode catalytic layer structure 300 includes a first catalytic layer 301, a second catalytic layer 302, and a third catalytic layer 303 between the first catalytic layer 301 and the second catalytic layer 302. The first catalytic layer 301 abuts the third catalytic layer 303, the third catalytic layer 303 abuts the second catalytic layer 302, and the second catalytic layer 302 abuts the proton exchange membrane 105. That is, the second catalytic layer 302 is positioned closer to the proton exchange membrane 105 of the MEA than the third catalytic layer 303, and the third catalytic layer 303 is positioned closer to the proton exchange membrane 105 of the MEA than the first catalytic layer 301.
The method of manufacturing the cathode catalytic layer structure 300 is different from the aforementioned method of manufacturing the cathode catalytic layer structure 200 in that the method of manufacturing the cathode catalytic layer structure 300 further includes forming a third catalytic layer 303 between the first catalytic layer 301 and the second catalytic layer 302, the third catalytic layer 303 being formed of a third slurry. As will be described in detail below, the inventors effectively improve the performance and lifetime of the MEA by adjusting the characteristics of the first, second and third catalytic layers 301, 302 and 303 by adapting various parameters of the first, second and third slurries to effectively mitigate the agglomeration of platinum-based catalyst particles and the corrosion of the carbon support on the cathode catalytic layer structure 300 while maximizing the proton conductivity, oxygen transport capacity and ECSA of the cathode catalytic layer structure 300, which would otherwise result in degradation of the performance and lifetime of the cathode catalytic layer structure 300.
Example 2:
example 2 differs from the foregoing example 1 in that in the production method of example 2, the first slurry, the second slurry, and the third slurry may be formulated so that the first slurry, the second slurry, and the third slurry, and the first catalytic layer 301, the second catalytic layer 302, and the third catalytic layer 303 have the following characteristic parameters: (1) The third average particle size of the third platinum-based catalyst in the third slurry is greater than the first average particle size and less than the second average particle size; (2) The third specific surface area of the third carbon support in the third slurry is greater than the second specific surface area and is greater than or equal to the first specific surface area (e.g., the third specific surface area may be greater than the first specific surface area); (3) The third I/C ratio in the third slurry is greater than the second I/C ratio and less than the first I/C ratio; (4) The weight of the third platinum-based catalyst in the third slurry is greater than or equal to 40% of the total weight of the third carbon support and the third platinum-based catalyst; and (5) the third platinum loading of the third catalytic layer 303 is at least twice the first platinum loading of the first catalytic layer 301 and at least twice the second platinum loading of the second catalytic layer 302.
The first, second and third catalytic layers 301, 302 and 303 formed of the first, second and third pastes having the above combinations of the characteristic parameters (1) to (5) can effectively reduce agglomeration of platinum-based catalyst particles and corrosion of the carbon support on the cathode catalytic layer structure 300 while maximizing proton conductivity, oxygen transport capacity and ECSA of the cathode catalytic layer structure 300, compared to a manufacturing method in which only one or some of the characteristic parameters are adjusted.
Specifically, for the cathode catalytic layer structure 300 having three catalytic layers, the second catalytic layer 302 is positioned closer to the proton exchange membrane 105 of the MEA than the first catalytic layer 301 and the third catalytic layer 303, and the first catalytic layer 301 is positioned closer to the cathode diffusion layer (not shown in fig. 3) than the second catalytic layer 302 and the third catalytic layer 303. During the electrochemical reaction, the oxygen transmission path from the cathode flow channel to the first catalytic layer 301 is shorter than the second catalytic layer 302 and the third catalytic layer 303, and thus the first catalytic layer 301 is easier to obtain sufficient oxygen. However, the proton conduction path from the proton exchange membrane 105 to the first catalytic layer 301 is longer than the second catalytic layer 302 and the third catalytic layer 303, and thus the amount of protons that the first catalytic layer 301 can obtain is limited. In addition, the degree of agglomeration of the platinum-based catalyst particles and corrosion of the carbon support on the second catalytic layer 302 is more severe than the first catalytic layer 301 and the third catalytic layer 303. By having the first, second and third catalytic layers 301, 302 and 303 formed of the aforementioned first, second and third slurries, respectively, it is possible to provide the first catalytic layer 301 with better oxygen transport capability and relatively large ECSA, the second catalytic layer 302 with better proton conductivity and ability to suppress agglomeration of platinum-based catalyst particles and corrosion of carbon carriers, and the third catalytic layer 303 with ECSA being maximized, thereby effectively reducing agglomeration of platinum-based catalyst particles and corrosion of carbon carriers on the cathode catalytic layer structure 300 while maximizing proton conductivity, oxygen transport capability and ECSA of the cathode catalytic layer structure 300. This can improve the performance and lifetime of the MEA, and thus the PEMFC.
Table 4 shows an exemplary implementation of embodiment 2.
TABLE 4 Table 4
In the exemplary implementation shown in table 4, the third average particle size of the third platinum-based catalyst in the third slurry is greater than the first average particle size of the first platinum-based catalyst in the first slurry and less than the second average particle size of the second platinum-based catalyst in the second slurry. Preferably, the first average particle size is less than 2nm, the second average particle size is greater than 4nm, and the third average particle size is between 2nm and 4 nm.
The third specific surface area of the third carbon support in the third slurry is greater than the second specific surface area of the second carbon support in the second slurry and is greater than or equal to the first specific surface area of the first carbon support in the first slurry. Preferably, the first specific surface area is 200m 2 /g to 800m 2 Between/g, a second specific surface area of 100m 2 /g to 200m 2 Between/g, and a third specific surface area of 800m 2 /g to 1000m 2 Between/g.
The third I/C ratio in the third slurry is greater than the second I/C ratio in the second slurry and less than the first I/C ratio in the first slurry. Preferably, the first I/C ratio is greater than 0.9 and less than or equal to 1.05, the second I/C ratio is less than or equal to 0.8, and the third I/C ratio is equal to 0.9.
The third platinum loading of the third catalytic layer is at least twice the first platinum loading of the first catalytic layer and at least twice the second platinum loading of the second catalytic layer. Providing such a platinum loading gradient may provide a maximum ECSA at the third catalytic layer 303, thereby locating the primary reaction zone at the third catalytic layer 303. Preferably, the total platinum loading of the first catalytic layer, the second catalytic layer and the third catalytic layer is in the range of 0.1-0.6mg/cm 2 。
In an additional example, the first slurry, the second slurry, and the third slurry may also be configured to additionally have the following characteristic parameters: the first ionomer in the first syrup has an EW value greater than the second ionomer in the second syrup and greater than the third ionomer in the third syrup, preferably the first ionomer has an EW value between 800g/mol and 1000g/mol, the second ionomer has an EW value between 720g/mol and 800g/mol, and the third ionomer has an EW value between 720g/mol and 800 g/mol. In this way, it is possible to ensure good proton conduction at the first catalytic layer 301 and the third catalytic layer 303, and to ensure good proton conduction and oxygen transmission at the second catalytic layer 302 at the same time.
Further, the thickness of each of the first catalytic layer 301, the second catalytic layer 302, and the third catalytic layer 303 is substantially the same. Preferably, the total thickness of the first catalytic layer 301, the second catalytic layer 302 and the third catalytic layer 303 is preferably 6 μm to 15 μm.
Comparative example 2:
a cathode catalytic layer structure formed from the slurries shown in table 5. It should be understood that the remaining parameters of the cathode catalytic layer structure, not listed, were consistent with those of the cathode catalytic layer structure 300 formed from the slurries shown in table 4 as a comparative example.
TABLE 5
In the accelerated aging test, a dynamic voltage square wave scan of 0.6 to 0.95V was applied to the cathode side for a period of 2s for a total cycle of 30000 turns. After 30000 cycles, the ECSA of the cathode catalytic layer structure 300 formed from the slurry shown in table 4 decreased by less than 30%, while the cathode catalytic layer structure of comparative example 2 exceeded 40%. It can be seen that the cathode catalytic layer structure 300 has higher durability and longer service life than the comparative example. The cathode catalytic layer structure 300 prepared by the preparation method provided by the application can effectively reduce platinum catalyst particle agglomeration and carbon carrier corrosion on the cathode catalytic layer structure 300 while maximizing the proton conductivity, oxygen transport capacity and ECSA of the whole cathode catalytic layer structure.
As described above, each of the first platinum-based catalyst, the second platinum-based catalyst, and the third platinum-based catalyst is selected from the group consisting of a pure platinum catalyst and a platinum-based alloy catalyst. The platinum-based alloy catalyst is a PtM catalyst, wherein M is a third period transition element (Ni, co, cr, mn, fe). Preferably, the first platinum-based catalyst, the second platinum-based catalyst, and the third platinum-based catalyst are the same platinum-based catalyst. It should be understood that the first platinum-based catalyst, the second platinum-based catalyst, and the third platinum-based catalyst may also be different platinum-based catalysts.
The cathode catalytic layer structure 200 and the cathode catalytic layer structure 300 may each be formed by a transfer method, a blade method, a spray method, a brush method, an inkjet printing method, or a slot die coating method using the respective aforementioned pastes. The transfer printing method is to prepare a cathode catalytic layer structure on a matrix membrane, then hot-press the matrix membrane with the cathode catalytic layer structure and a proton exchange membrane, and transfer the cathode catalytic layer structure on the matrix membrane to the proton exchange membrane. The blade coating method is a method of manufacturing an MEA by a blade coating process, that is, a surplus slurry is scraped off with a set gap by a blade, thereby obtaining a cathode catalyst layer of a predetermined thickness. For example, the foregoing slurry may be layered directly on the proton exchange membrane 105 by a direct blade coating method. The spraying method refers to spraying the slurry directly onto the proton exchange membrane 105. The brushing method is to brush the slurry on the proton exchange membrane 105. The inkjet printing method refers to printing the aforementioned slurry on, for example, the proton exchange membrane 105 using an inkjet printing apparatus. The slot-die coating method refers to a method in which the aforementioned slurry is simultaneously and hierarchically stacked on the proton exchange membrane 105 through two or more slot dies to form a cathode catalytic layer structure. It will be appreciated that other parameters or components of the foregoing slurry than the foregoing characteristic parameters may be adjusted to render the slurry suitable for forming a cathode catalytic layer structure by these methods.
It should be understood that the foregoing slurry may include other components such as deionized water, dispersants, modifiers, and the like in addition to the platinum-based catalyst, carbon support, ionomer, but the present application is not limited thereto.
It should also be understood that the preparation method according to the application can also be used to manufacture cathode catalytic layer structures of more than three layers, but the application is not limited thereto.
It should also be understood that the terms "first," "second," "third," and the like are used merely to distinguish one parameter or material from another parameter or material, but that such parameters and/or materials should not be limited by such terms.
The application has been described in detail with reference to specific embodiments thereof. It will be apparent that the embodiments described above and shown in the drawings are to be understood as illustrative and not limiting of the application. It will be apparent to those skilled in the art that various modifications or variations can be made in the present application without departing from the spirit thereof, and that such modifications or variations do not depart from the scope of the application.

Claims (10)

1. A method of preparing a cathode catalytic layer structure of a membrane electrode assembly of a fuel cell, the method comprising forming a cathode catalytic layer structure having at least a first catalytic layer and a second catalytic layer for positioning closer to a proton exchange membrane of the membrane electrode assembly than the first catalytic layer, the first catalytic layer being formed from a first slurry and the second catalytic layer being formed from a second slurry, wherein:
the first average particle size of the first platinum-based catalyst in the first slurry is less than the second average particle size of the second platinum-based catalyst in the second slurry;
the first specific surface area of the first carbon support in the first slurry is greater than or equal to 200m 2 And a second specific surface area of the second carbon support in the second slurry of 200m or less 2 /g；
The first I/C ratio in the first slurry is greater than 0.9, and the second I/C ratio in the second slurry is less than or equal to 0.9; and
the first weight percentage of the first platinum-based catalyst in the first slurry is 40% or more of the total weight of the first carbon support and the first platinum-based catalyst, and the second weight percentage of the second platinum-based catalyst in the second slurry is 40% or less of the total weight of the second carbon support and the second platinum-based catalyst.
2. The method of claim 1, wherein the first slurry and the second slurry are in at least one of the following forms:
the first average particle diameter is 2nm or less, and the second average particle diameter is 2nm or more;
the first specific surface area is 800m 2 /g to 1000m 2 Between/g, and the second specific surface area is 100m 2 /g to 200m 2 Between/g;
the first I/C ratio is greater than 0.9 and equal to or less than 1.05, and the second I/C ratio is equal to 0.9, preferably equal to or less than 0.8;
the first weight percent is between 50% and 60%, and the second weight percent is between 20% and 40%.
3. The method according to claim 1, characterized in that:
the first platinum loading of the first catalytic layer is at least 1.5 times the second platinum loading of the second catalytic layer, the total platinum loading of the first catalytic layer and the second catalytic layer preferably being in the range of 0.1-0.6mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The thickness of the first catalytic layer and the thickness of the second catalytic layer are substantially the same, and the total thickness of the first catalytic layer and the second catalytic layer is preferably 6 μm to 15 μm.
4. The method of claim 1, wherein a first ionomer EW value in the first slurry is greater than a second ionomer EW value in the second slurry, preferably the first ionomer EW value is between 800g/mol and 1000g/mol, and the second ionomer EW value is between 720g/mol and 800 g/mol.
5. The method of claim 1, wherein forming the cathode catalytic layer structure further comprises forming a third catalytic layer between the first catalytic layer and the second catalytic layer, the third catalytic layer formed from a third slurry, wherein:
a third average particle diameter of a third platinum-based catalyst in the third slurry is greater than the first average particle diameter and less than the second average particle diameter;
a third specific surface area of a third carbon support in the third slurry is greater than the second specific surface area and is greater than or equal to the first specific surface area;
a third I/C ratio in the third slurry is greater than the second I/C ratio and less than the first I/C ratio;
the weight of the third platinum-based catalyst in the third slurry is greater than or equal to 40% of the total weight of the third carbon support and the third platinum-based catalyst; and
the third platinum loading of the third catalytic layer is at least twice the first platinum loading of the first catalytic layer and at least twice the second platinum loading of the second catalytic layer.
6. The method of claim 5, wherein the first slurry, the second slurry, and the third slurry are in the form of at least one of:
the first average particle size is less than 2nm, the second average particle size is greater than 4nm, and the third average particle size is between 2nm and 4 nm;
the first specific surface area is 200m 2 /g to 800m 2 Between/g, the second specific surface area is 100m 2 /g to 200m 2 Between/g, and the third specific surface area is 800m 2 /g to 1000m 2 Between/g;
the first I/C ratio is greater than 0.9 and equal to or less than 1.05, the second I/C ratio is equal to or less than 0.8, and the third I/C ratio is equal to 0.9;
the first ionomer EW value in the first syrup is greater than the second ionomer EW value in the second syrup and greater than the third ionomer EW value in the third syrup, preferably the first ionomer EW value is between 800g/mol and 1000g/mol, the second ionomer EW value is between 720g/mol and 800g/mol, and the third ionomer EW value is between 720g/mol and 800 g/mol.
7. The method according to claim 5, wherein:
the total platinum loading of the first catalytic layer, the second catalytic layer and the third catalytic layer is 0.1-0.6mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The thickness of each of the first, second and third catalytic layers is substantially the same, and the total thickness of the first, second and third catalytic layers is preferably 6 to 15 μm.
8. The method of claim 5, wherein each of the first, second, and third platinum-based catalysts is selected from the group consisting of a pure platinum catalyst and a platinum-based alloy catalyst, preferably the first, second, and third platinum-based catalysts are the same platinum-based catalyst.
9. The method according to any one of claims 1 to 8, wherein the cathode catalytic layer structure is formed by a transfer method, a blade method, a spray method, a brush method, an inkjet printing method, or a slot die coating method.
10. A cathode catalytic layer structure for a membrane electrode assembly of a fuel cell, characterized in that the cathode catalytic layer structure is prepared by the method according to any one of claims 1 to 9.
CN202210409434.1A 2022-04-19 2022-04-19 Cathode catalytic layer structure for membrane electrode of fuel cell and preparation method thereof Pending CN116960369A (en)

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